Certain water-soluble high molal oxyalkylated esters and method of making same



Patented Sept. 28, 1943 CERTAIN WATER-SOLUBLE HIGH MOLAL OXYALKYLATED ESTERS AND METHOD F MAKINGrSAME Melvin De Groote, University City, and Bernhard Keiser, Webster Groves, Mo., assignors to Petrolite Corporation, Ltd., poration of Delaware Wilmington, Del, a cor- No Drawing. Original application March 21, 1941,

Serial No. 384,601; Divided and this application June 26,1942, Serial N0. 448,687

11 Claims. (01. 260-44048) This invention, relates to a new chemical product or compound, our present application being a division of our co-pending application Serial No. 384,601, filed March 21, 1941, now

U. S. Patent No. 2,295,169, dated September 8,

One object of our present invention is to provide a new material, compound or composition of matter, that is capable of use for various purposes, and particularly adapted for use as a demulsifier in the resolution of crude oil emulsions; Another object of our invention is to provide a practicable method for manufacturing said new material, compound or composition of matter. The new chemical compound or composition of matter which constitutes our present invention is exemplified by the acid, or preferably, neutral esterderived by complete esterification of one mole of a polyalkylene glycol of the kind herein- 1 HOOC.D.COO.T' The polyethylene glycol may be characterized by materials of the kind such as heptaethylene glycol, octaethylene glycol, nonaethylene glycol,

.decaethylene glycol, to and including heptadec'aethylene glycol. For convenience, these polyethylene glycols may be indicated by the following formula: OH (C2H4Q) mI'I in which m varies from? through 17.

Instead of polyethylene glycols, one may use polypropylene glycols or polybutylene glycols. Thus, for convenience, in the broadest aspect, the polyalkylene glycols employedmay be indicated by the following formula:

inwhich m has its previous significance and n represents a numeral varying from 2 to 4.

" Thus, the bulk of the materials herein contemplated, particularly for use as demulsifiers, maybe indicated within certain variations, as hereinafter stated, bythe neutral ester derived by esterification of one mole of a glycol of the kind aboveLdescribed, with two, moles. of .a fractional'ester of the kind previously indicated; The formation of thecompound may be indicatedby the following reaction, although obviously, is immaterial. what particular; procedure is employed to produce the particular chemical compound or product:

indicated previously, the polybasic acids employed, are limited tothe type having not more than six carbon atoms, for example, oxalic, malonic, succinic, glutaric, and adipic. Similar- 1y, one may employ acids such asfumaric, maleic, glutaconicyand various others, including citric, malic, tartaric, and the like. The selection of the particular tribasic or dibasic acid employed is usually concerned largely with convenience of manufacture of the finished ester, and also of the price of thereactants. Generally speaking, the higher the temperature employed, the easier it is to obtain large yields of the esterified product. Although oxalic acid is comparatively cheap, it decomposes somewhat readily at slightly above the boiling point of; water. For this reason, it is more desirable to use an acid which is more resistant to'pyroly sis. Similarly, when a polybasic acid is available in the form of an anhydride, such anhydride is apt to produce the ester with greater ease than theacid itself. For this reason, 'maleic anhydride is particularly adaptable; and also, everything else considered, the cost is comparatively low on a per molar basis, even though somewhat higher ona per pound basis. 'Succinic acid or the anhydride has many of the attractive qualities of maleic' anhydride and this is also true ofadipic acid. For purposes of brevity, the bulk of the compounds hereinafter illustrated will refer to the use; of maleic anhydride, although ittis understood tha t any other suitable polybasic acid maybeemployed. ..Furthermore, for purposes of convenience, reference is made to the use ofpolyethylene glycols. As has been previouslyindicated such glycols can be replaced by suitable polypropylene or polybutylene comp und Y,

: As far as the range of oxyalkylated compounds employed asreactants isconcerned, it is our preference. to employthose having approximately 8-12 oxyalkylenegroups, particularly 8 -12 oxyethylenev groups; ;The preference to use the oxyethylate'd compoundsis due largely'lto the 'fact pounds are neutral or complete esters, as differentiated from fractional esters. The polyhydric alcohols employed as reactants for the production of the neutral estersof the high molal hydroxy acids, are characterized by the fact that they may contain 2, 3 or 4 hydroxyl groups, the

commonest examples being ethylene glycol,

Such glycolsrpresent the upper range of distillable glycols; and they maybe conveniently referred to as upper distillabl'e ethylene glycols. There is no particularly good procedure for making a sharper separation on a commercial scale; and it is understood that mixtures of one or more of the glycols may be employed, as well as a single glycol. As pointed out, it is particularly preferred to employ nonaethylene glycol as com:

mercially available, although it is understood that. this product contains other homologs, as indi cated.

Substantially as desirable as the upper distillable polyethylene glycols, are the lower nondistillable polyethylene glycols. These materials are available in the form of a waxy water-soluble material, and the general range may vary somewhat from decatotetradeca-ethylene glycol. As is well understood, the method of producing such glycols would cause some higher homolo'gs to be formed; and thus, even in this instance there may be present some oxyethylene glycols within the higher range above indicated. One need not point out that these particular compounds consist of mixtures, and that in some instances, particularly desirable esters are obtained by making mixtures of the liquid nonaethylene glycol with the soft, waxy, lower non-distillable polyethylene glycols. For the sake of convenience, reference in the examples will be to nonaethylene glycol; and calculations will be based on a theoretical molecular weight of 414. Actually, in manufacture, the molecular weight of the glycol employed, whether a higher distillable polyethylene glycol or a lower nondistillable polyethylene glycol, or a mixture of the same, should be determined and reaction conducted on the basi of such determination, particularly in conjunction with the hydroxyl or acetyl value.

It has been previously pointed out that it is immaterial how the compounds herein contemplated are manufactured, although we have found it most desirable to react the selected glycol or mixtures of glycols with maleic anhydride in a ratio of two moles of the anhydride for one mole of the glycol. Under such circumstances, we have found little tendency to form longer chain poly mers; and in fact, the product of reaction, if conducted at reasonably low temperatures, appears to be largely monomeric. For convenience, such intermediate product may then be considered as a dibasic or polybasic acid. One mole of the intermediate so obtained is then reacted with two moles of the alcoholic material of the kind subsequently described.

It is to be noted, however, that if one prepares a fractional acidic ester, then if two moles of the fractional acidic ester are reacted with one mole of the polyethylene glycol, there is no possibility of the formation of polymeric types of esterification products under ordinary conditions.

The alcoholic products employed as reactants in the manufacture of the present compounds are water-insoluble hydroxylated esters of polyhydric alcohols, characterized by being derived from high molal hydroxy acids and also by the fact that there is no residual hydroxyl radical attached to the alcohol residue, i. e., the comglycerol andpentaerythritol. Other dihydric a1- coholsfiriclud'ei homologs of ethylene glycol, such as propylene glycol, butylene glycol, etc., and include higher homologs. Still another variety is illustrated bythe ether type of glycol, such as diethylene glycol, dibutylene glycol, etc. It is not "intended to include ether alcohols, particularly ether glycbls, in which the ether linkage occurs more than-four times. Dihydric alcohols are also obtained by dehydroxylation of glycerol or the like, as, for example, by etherization with a monohydric alcohol; for instance, the methyl ether,

ethyl ether, propyl ether, butyl ether, and similar alkoxy derivatives of glycerol. Trihydrio alcohols are illustrated most advantageously by glycerol; Similarly; etherization with monoliy dric alcohols yields trihydric alcohols from reducts such as diglycerol, pentaerythritol, manni tan, sorbitan, etc. The ethyl ether, butyl ether, or other alkoxy derivatives of diglycerol-ls an additional illustration ofthis particular type. Alcohols containing four hydroxyls may be illustrated by diglyc'erol, pent'aerythritol, 'sorbitan, mannitan, etc.

The polyhydr'ic alcohols just described are ester-ified with or converted by any suitable means into water-insoluble esters of high molal hydroxy acids having at least 11 carbon atoms and not in excess of 36 carbon atoms. The coinmonest example of a high molal hydroxy acid is ricinoleic acid. Other liy'droxy fatty acids include hydroxystearic' acid, dihydroxystearic acid, diricinoleic' acid, aleuritic acid, and the like. Sinfilar'acids are obtained in the oxidation of paramn, etroleum hydrocarbons, o'r wax, and are commonly referred to as hydroxylated wax acids. Hydroxylated wax acids occur as byproducts in the oxidation of waxes or similar materials and are usually separated so that the commonest commercial form of oxidized wax acids represent mixtures comparatively free from the hydroxylated compounds. Hydroxylated acids are produced by other procedures, such as chlorination, either by addition or substitution, as, for example, chlorination of oleic acid or stearic acid. Subsequent reactions involve the removal of the chlorine with the introduction of a hydroxyl radical. Undecylenic acid, derived from castor oil, has been converted into a by droxy undecenoic acid. Unsaturated hydroxy acids, such as ricinoleic acid, may be treated in various manners, so as to produce derivatives, for example, chlorinated or brominated rici'noleic acid. Such materials are entirely satisfactory for use as reactants in 'the'preparation of mate-'- rials of the kind herein contemplated. Naturally-occurringnaphtlienic acids can also be con verted into hydroxylated productsby' following similar procedure. Ah unsaturated hydroxy acid, such as ricinoleic acid,- can be converted into a hydroxylated arylstearic acid. Such procedure contemplates reactions such as those involving ricinoleic acid, benzene, and aluminum chloride in large excess, or involves the desulfonation of a'sulfo-aromatic fatty acid. In any event, by involving derivatives of undecylenic acid, or one or-more-ofthe various wax acids, naturally-ochydroxyl.

Hydroxy acids of the kind herein contemplated may also be prepared by the hydrolysis of alpha-halogen acids. For instance, alpha-bromocaproic acid, alpha-bromocaprylic,acid, alphabromocapric acid, alpha-bromolauric-acid, alphabromomyristic acid, alpha-bromopalmitic acid,

and the like, can be hydrolyzed to give the corre- I sponding alpha-hydroxy acid. Indeed, a reactive alpha-halogen acid may serve as a functional equivalent of an alpha-hydroxy acid by liberation of hydrochloric acid, instead of water. Such type of reaction, however, involves numerous difliculties; and thus, it is better to employ a hydroxy acid.

In some instances derivatives ofa hydroxylated unsaturated acid are most readily obtained by the employment of an intermediate in which the hydroxyl group is protected. Thus, ricinoleic acid may be acetylated, and such acetyl ricinoleic acid converted into a derivative, for instance, a derivative in which an aryl group is introduced. Such derivative can then be saponified or hydrolyzed so as to regenerate the hydroxyl radical. As to the manufacture of various esters from acids of the kind above described, attention is directed. to the following United States'patents: Nos. 1,160,595, dated Nov. 16', 1915, to Gruter et 21.1.; 2,221,674, dated Nov. 12, 1940, to Ellis; 2,177,407, dated Oct. 24, 1939, to Hansley. See also Organic Syntheses, volume X, page 88, 1930.

, AcInIo INTERMEDIATE PRonucT.Ea:ampZe 1 One pound mole of nonaethylene glycol is reacted with two pound moles of maleic anhydride so as to form nonaethylene glycol dihydrogen dimaleate. I

ACIDIC INTERMEDIATE PRODUCT.-E.'Edm1)l6 2 ACIDIC INTERMEDIATE PROnUoT.-ExampZe 3 The same procedure is followed as in Intermediate product, Examples 1' and 2, except that the molar ratio of maleic anhydride to glycol is changed so that three pound moles of maleic anhydride are reacted with two pound moles of the glycol, so as to yield a dibasic product which may be conveniently described as a further elaboration of the monomeric derivative describedin preceding Examples '1 and 2. Such polymers form very slowly, and require higher tempera- :ture, and a comparatively longer period of, reaction time. Also it is desirable to add 'a small fraction of a suitable catalyst, say, one fourth of 1% of toluene sulfonic acid, and to pass a dried inert gas through the reaction mass.

ACIDIC INTERMEDIATE PRnuoT.ExampZe 4 Adipic acid is substituted for maleic anhydride in Examples 1 -3,'preceding.

VACIDIC INTERMEDIATE PROnUoT-.Emample 5 Oxalic acid is substitutedfor maleic anhydride i Examples 1+ p eced ng. r

AcInIc'INTEaMnn ATE Paonuor-Example 6 Citric acid is substituted for maleic anhydride,

in Examples 1-3,,preceding,-

AcInIo I TERMEnIA n PnonncrA-Erample 7 Succinic anhydride is substituted for maleic anhydride in Examples 13, preceding.

COMPOSITI N or MATTER.E$ampZ6 1 A one pound mole of the intermediate product .Of the kind described in Intermediate products, Examples 1, 2 and 3, above, is reacted with two pound moles of ethylene glycol diricinoleate until substantially all .dibasic carboxyl acidity has disappeared. Time of reaction may vary from a few hours to as much as 20 hours.

CoMPosITIo or ItIAT EEQEacampZe 2 Ethylene glycol dithydroxyste'aratel is substituted for ethylene glycol diricinoleate in the preceding example; I

ICOMPOSITIONOF MATTER; E.Tample 3 Di-ethylene glycol diricinoleate is substituted for ethylene glycol diricinoleate III'COmDOSitiOII of matter, Example 1. I

COMPOS TION or Merriam-Example Dipropylene glycol diricinoleate is substituted for ethylene glycol diricinoleate in Composition of matter, Example 1'.

COMPOSITION F MATTER. E.rample 5.

Glyceryl alpha-,monomethyl ether diricinoleate is substituted for ethylene glycol diricinoleate in Composition of Matter, Example '1.

CO P sI TION or MA TE a.E mmpZe 6 Glyceryl alpha-mononormal butyl ether diricinoleate is substituted for ethylene glycol diricinoleate in Composition of matter, Example 1.

CQMPOSITIQN OF MATTER.-E.mmple 7 Glyceryl alpha-monoisoamylether diricinoleate is substituted for ethylene glycol diricinoleate in Composition of Matter, Example 1.

COMPOSITION OF MATTER-Example 8 v Glyceryl alpha-monophenyl ether diricinoleate is substituted for ethylene glycol diricinoleate in Composition of matter, Example 1.

COMPOSITION or MATTER.Example 9 In Composition of matter, Examples 1-8 pre-- ceding, any residual acidity present is removed by cautiously adding a dilute solution of ammonium hydroxide until the resultant product gives a clear, limpid solution in water, particularly in dilute form. I

' I COMPOSITION or MATTER.-EwampZe 10 In Composition of matter, Examples 1-8, preceding, any residual acidity present is removed by cautiously adding a dilute solution of triethanolamine until the resultant product gives a clear, limpid solution in-water, particularly in dilute form.

COMPOSITION OF MATTERE.L'amf0Z6 11 CoMPosr'rIoN OF MATTER-Example 12 The same procedure is followed as in Composition of matter, Examples l-ll inclusive, except that an intermediate product of the kind exemplified 'by Intermediate product, Example 4, is substituted for that in Intermediate product, Examples 1, 2 and 3.

COMPOSITION or MA'r'rER-E:rample 13 The same procedure is followed as in Composition of matter, Examples 1-11, inclusive, except that an intermediate product of the kind exemplified by Intermediateproduct, Example 5, is substituted for that inlntermediate product, Examples 1, 2 and 3.

COMPOSITION or MArrERE:rample 14 COMPOSITION or mrrnR-Exomple 15 The same procedure is followed as in Composition of matter, Examples 1-11, inclusive, ex- .cept that an intermediate product of the kind exemplified by Intermediate product, Example 7., is substituted for that in Intermediate product, Examples 1, 2 and 3.

It is to be noted that this second step is an esterification reaction, and the same procedure is employed as suggested above in the preparation of the intermediate product. Needless to say, any particular method may be used to produce the desired compounds of the kind indicated. In some instances it may be desirable to conduct the esterification reaction in the presence of a non-volatile inert solvent which simply acts as a diluent or viscosity reducer.

In the preceding examples, attention has been directed primarily to the monomeric form, or at least, to the form in which the bifunctional alcohol, i. e., a glycol, and the polyfunctional acid, usually a bifunctional compound, react to give a chain type compound in which the adjacent acid and glycol nucleus occur as a structural unit. For instance, in the the monomeric form this may be indicated in the following manner:

acid glycol acid If, however, one prepared an intermediate product employing the ratio of three moles of I Similarly, three moles of the glycol and four moles of the acid might tend to give a combination which may be indicated thus:

acid. glycol acid glycol acid glycol acid Another way of stating the matter is that the composition may be indicated in the following manner:

'roocpooo[(CHl0),..-1G1Hlooonooolzr in which the characters have their previous sig nificance and at is -a relatively small whole number less than 10, and probably less than and in the monomeric form :r, of course, is "I l-1e limitations on the size of :c are probab1 y infiu enced largely by the' fa'c't that reaction leading to" further growth is dependent upon random contact. ,Some of the products are self-emulsifiable oilsor self-emulsifiable compounds, whereas, others give cloudy solutions or sols; and the most desirable type is characterized by givinga clear solution in water, and usually in the pres- I ence of soluble calcium or magnesium salts, and

frequently, in the presence of significant amounts oieither acids or alkalies.

Water solubility can be enhanced in a number of ways which have been suggested by previous manufacturing direction, for instance:

(a) By using a more highly polymerized ethylene glycol;

- lb) By using. a polymeric form instead of a monomeric form in regard to the unit which forms the chain between the two alcoholic nuclei; I

(c) By using a polybasic carboxy acid of lower molecular weight, for instance, maleic acid, instead of adipic acid;

(d) By using an alcoholic material of lower molecular weight, for instance, a ricinoleic acid ester, instead of the ester of a hydroxylated wax acid of a higher molemilar weight.

In any event, it is to benoted that the compounds oi the type herein contemplated are limiated to the water-soluble type, i. e., those which are self-emulsifying. in Water, or produce a sol or'a molecular solution.

Actually, a reaction involving an alcohol and an acid (esterification) may permit small amounts of either one or both of the reactants, depending upon the predetermined proportion, to remain in an unreacted state. In the actual preparation of compositions of the kind herein contemplated, any residual acidity can be removed by any suitable base, for instance, ammonia, triethanolamine, or the like, especially in dilute solution. Naturally, precaution should be taken so that neutralization takes place without saponification or decomposition of the ester. In some cases there is no objection to the presence of the acidic group. Indeed, if a tribasic acid be employed in such a manner as to leave one free carboxyl group, then it is usually desirable to neutralize such group by means of a suitable basic material;

In the hereto appended claims, reference to a neutral product refers to one in which free carboxylic radicals are absent.

Materials of the kind herein contemplated may find uses as wetting, detergent, and leveling agents in the laundry, textile, an dyeing induse try; as wetting agents and detergents in the acid washing of fruit, in the acid washing of building stone and brick; as a wetting agent and spreader in the application of asphalt in road building and the like, as a constituent of soldering flux preparations; as a flotation reagent in the note? tion separation of various minerals; for flocculation and coagulation of various aqueous suspen'. sions containing negatively charged particles .such as sewage, coal washing waste water, and various trade wastesland the like; as germicides, insecticides, emulsifiers for cosmetics, spray oils, water-repellent textile finish, etc. These uses are by no means exhaustive.

However,. the most important phase of the present invention, as far as industrial application goes, is concerned with the use of materials of the kind previously described as demulsifiers for water-in-oil emulsions, and more specifically, emulsions of water or brine-in crude petroleum.

We have found that the particular chemical compounds or reagents herein described and'desirable for useas demulsifiers', may also beused for other purposes, for instance; as abreak inducer in doctor treatment of'the kind intended to sweeten gasoline. See U. S. Patent" No. 2,157,223, dated May- 9, 1939;to Sutton.

Chemical compounds of thekindherein 'described are'also of value as surface'- tension depressants in the acidification of calcareous oil'- bearing strata by means of strong'mineral acid, such as hydrochloricacid. Similar-1y, some mem bers are efiective as surface tension depressants or wetting agents in the floodingo'f'exliausted oil-bearing strata.

As to using compounds-of the kind herein deprocedure described in detail in U. SQPatent No.

2,226,119, dated December 24, 1940, to De Groote and Keiser. As to using compounds of the kind herein described as demulsifiers, or in particular as surface tension depressants, in combination withmineral acid or acidization of oil-bearing strata, reference is made to U. S. Patent No. 2,233,383, dated February 25, 1941, to De Groote and Keiser.

It will be apparent to those skilled in the art that residual carboxyl acidity can be eliminated by esterification with a low molal alcohol, for instance, ethyl, methyl, or propyl alcohol, by conventional procedure, so as to give a substantially neutral product. The introduction of such low molal hydrophobe groups does not seriously aiTect the solubility, and in some instances, gives increased resistance, to soluble calcium and magnesium salts, for such property is of particular value. Usually, however, neutralization with a dilutesolution of ammonia or the like is just as practicable and less expensive. 7

Having thus described our invention, what We claim as new and desire to secure by Letters Patent is:

1. A water-soluble ester, being the resultant acid having not more than 6 carbon atoms; and

the ratio of said primary esterifying reactants being within the range of more than 1 mole and not over 2 moles of thepolybasic acid for each mole of the polyalkylene glycol; and the said intermediate alcoholic reactant being the complete Water-insoluble ester of two additional reactants, andlikewise, one being acidic and the other alcoholic, to wit, a high molal monocarboxy hydroxy acid having at least 8 and not more than 32 carbon atoms, and a polyhydric alcohol, the

alcohol radical of said complete ester having a valency of at least 2 and not more than 4; the ratio of said intermediate reactants being at least 1 mole of the acidic intermediate reactant per mole of the alcoholic intermediate reactant and not more moles of the intermediate acidic reactant than the aforementioned valency of the alcoholic ester radical.

2. A water-soluble ester, as defined in claim 1,

-with-the added proviso'that: said ester must-be neutral. 1 g

3. A water-soluble ester, as defined in claim 1, with the added proviso that said ester must be neutral, and that'the polybasic primary reactant 'bea dibasic carboxy acid having not over'fi carbon atoms. I 'f i :r"4:,. A water-soluble ester; as defined in claim 1, ,With theadded' proviso that 'said'ester must vbe neutral; that the polybasic primary reactant be a, dibasic carboxy acidhaving not over 6 carbon atoms; and the primary polyglycol reactant being a polyalkylen'e glycol having at least-'7 and not more than 1'7 ether linkages. i s

5; A water soluble ester, as defined in claim 1, with the added proviso that said ester must be neutral; that the polybasic primary reactant be a dibasic carboxy acid having not over 6 carbon atoms; the primary polyglycol reactant being a polyalkylene glycol having at least 7 andnot more than 1'7 ether linkages; and the acyl radical of the high molal monocarboxy hydroxy acid containing 18 carbon atoms.

' 6. A neutral water-soluble chemical com pound, as defined in claim 1, and of the following structure formula:

TOOC.D.COO[ (021-) CzHiOOCDCOO :rT

in which T is a diol ricinoleate radical; and D is the dibasic acid residue; and m represents a numeral varying from 7 to 12.

8. A neutral water-soluble chemical compound, as defined in claim 1, and of the following structural formula:

in which T is a diol ricinoleate radical; and D is a maleic acid residue; and m represents a numeral varying from 'I to 12.

9. A neutral water-soluble chemical com pound, as defined in claim 1, and of the following structural formula:

in which 'I is a diol ricinoleate radical; and D is a succinic acid residue; and m represents a numeral varying from 7 to 12.

10. A neutral water-soluble chemical compound, as defined in claim 1, and of the following structural formula:

. in which T is a diol ricinoleate radical; and D is an adipic acid residue; and m represents a numeral varying from '7 to 12.

11. In the manufacture'of a water-soluble ester, being the resultant of two intermediate reactants, to wit, an acidic intermediate reactant and an alcoholic intermediate reactant; said acidic intermediate reactant being in turn the resultant fractional ester of two primary reactants, one being alcoholic and the other acidic; said primary alcoholic reactant consisting of a polyalkylene glycol having at least 7 and not i more than 17 ether linkages; and the alkylene radical thereof containing at least 2 and not more than '6 carbon atoms; and the acidic pri-- mary reactant being a polybasic carboxy acid having not more than '6 carbon atoms; and, the ratio of said primary esterifying reactants being within the range of more than 1 mole and :not over 2 moles of the polybasic acid for each mole of the polyalkylene glycol; and the said intermediate alcoholic reactant being the complete water-insoluble ester of 'two additional reactants, and likewise, one being acidic and the other alcohclic, to wit, a "high molal monocarboxyihydrcxy acid having at least Band not more than 32 carbon atoms, and a pclyhydric alcohol, the alcohol radicalof said ester having avvalency of at least 2 and not more than 4; the ratio of said intermediate reactants being at least- 1 mole of the acidic intermediate reactant permole of the alcoholic intermediate reactant and not more moles of the intermediate acidic reactant than the aforementioned valency of the alcoholic ester radical; the steps of: (A) esterifying the polyhydric alcohol with the high molal monocarrbcxyrhydroxy acid to yield the alcoholic intermediate; (B) reacting the polyalkylene glycol with the polybasic acid to yield the acidic intermediate reactant; and (C) subsequently reacting said intermediate reactants to yield acwa tar-soluble ester.

MELVIN DE GROO'I'E.

BERNHARD KEISER. 

